Phosphate-free carboxylate-sulfate detergents

ABSTRACT

Detergent-active materials having low fish toxicity suitable for heavy duty laundering in the absence of builders comprising sulfated gylcol or polyglycol half esters of alkyl or alkenyl succinic acids, or water-soluble salts thereof, wherein the alkyl or alkenyl group contains from about 14 to about 22 carbon atoms, the glycol moiety of the ester contains from 1 to 4 units of 2 to 4 carbon atoms, and the sulfate group is terminally attached to the glycol or polyglycol chain.

United States Patent [1 1 Danzik et al.

1451 Dec. 2, 1975 l PHOSPHATE-FREE CARBOXYLATE-SULFATE DETERGENTS [75]Inventors: Mitchell Danzik, Pinole; Ralph House, El Sobrante, both ofCalif.

[73] Assignee: Chevron Research Company, San

Francisco, Calif.

'22 Filed: July 11, 1974 [21] Appl. No.: 483,261

Related U.S. Application Data [62] Division of Ser. No. 259,924, June 5,I972, Pat. No.

[52] U.S. Cl. 260/458 [5 1] Int. Cl. C07C 141/02 [58] Field of Search260/458 [56] References Cited UNITED STATES PATENTS 3,086,043 4/l963Gaertner 2 60/5l 3 R 3,689,532 9/1972 Emmons ct al 260/458 PrimaryExaminerJames 0. Thomas. Jr.

Assistant ExaminerNicky Chan Attorney, Agent, or FirmG. F. Magdeburger;John Stoner. Jr.; J. T. Brooks [57] ABSTRACT Detergent-active materialshaving low fish toxicity suitable for heavy duty laundering in theabsence of builders comprising sulfated gylcol or polyglycol half estersof alkyl or alkenyl succinic acids, or watersoluble salts thereof,wherein the alkyl or alkenyl group contains from about 14 to about 22carbon atoms, the glycol moiety of the ester contains from i to 4 unitsof 2 to 4 carbon atoms, and the sulfate group is terminally attached tothe glycol or polyglycol chain.

: 4 "Claims, N0 Drawings PHOSPHATE-FREE CARBOXYLATE-SULFATE DETERGENTSBACKGROUND OF THE INVENTION This is a division of application Ser. No.259,924, filed June 5, 1972, now U.S. Pat. No. 3,843,707.

This application is directed to detergent active materials which may beincorporated into detergent formulations which are capable of being usedfor heavy duty laundering without the presence of eithereutrophication-causing or highly alkaline materials which are harmful tohuman tissue. In addition, these detergent active materials possessother virtues, the combination of which is unique in the detergent area.Thus the compounds are both aerobically and microaerophilicallybiodegradable and possess low (exceptionally low with certain species ofthe compounds) fish toxicity properties.

As is well known, in the United States accelerated concern for theprotection of the environment has re sulted in efforts by the concernedbranches of Government and the detergent industry to eliminate phosphatebuilders from detergent compositions because of the fear of suspectedeutrophication believed to be caused by the phosphates in the currentlyused detergent formulations. The precipitous introduction and marketingof many hurriedly formulated phosphate-free compositions has, however,raised the spectre of the cure being possibly worse than the illness dueto the caustic nature of many of the formulations. The necessity ofincluding some builder in the formulations as a replacement for thephosphates in order to achieve sufficient detergency has resulted inthese formulations being compounded with such materials asmeta-silicates and carbonates making the danger of skin, eye, and mucousmembrane damage to persons who use the formulations a substantial one.Thus the Federal Government has required that several of the newdetergent formulations be labeled as hazardous substances and theSurgeon General of the United States has recently recommended thathousewives continue to use phosphatecontaining detergents for thepresent as being the lesser of evils.

In addition to the corrosive properties of many of the new detergentformulations, despite claims to the contrary, many of them have notproved to be effective replacements for conventional heavy dutydetergents in terms of their ability to remove soil from fabrics andprovide clean-appearing clothes, etc.

An additional problem with more conventional detergents and'which existsas well with most of the newly introduced non-phosphate detergentcompositions is the fact that while they may be aerobicallybiodegradable with secondary disposal plants, they are not easilydegradable under microaerophilic conditions such as are encountered inareas where septic tanks and cesspools provide the means of sewagedisposal. This results in substantial quantities of undegradedsurface-active materials being discharged into water sources and hasresulted in certain areas in Government bans on all laundering agentsexcept for soap.

There exists, therefore, a pressing need for detergentactive materialswhich may be compounded without phosphate builders and without causticbuilders, which are biodegradable and are degradable under conditionsencountered in septic tanks and cesspools and which will have minimaleffect on marine organisms if dis- 2 charged by design or accident intorivers and lakes. etc. Thus the detergent actives should not exhibithigh toxicity to fish, etc.

PRIOR ART U.S. Pat. No. 3,086,043 discloses as surface active materialscompounds of the formula COOH R in which R is alkenyl of 8 to 20 carbons(preferably branched), R is lower alkyl of 1 to 4 carbon atoms orhydrogen, x is O to 3, and Z is a salt forming cation. The compounds areformed by reacting a hydroxy-containing sulfonate such as sodiumisethionate with alkenyl succinic anhydride.

SUMMARY OF THE INVENTION Detergent active materials capable of beingformulated into compositions which are suitable for heavy dutylaundering in the absence of phosphate builders or such highly causticbuilding materials as carbonates, meta-silicates, etc., are provided.The detergent active materials are easily biodegraded, both aerobicallyand microaerophilically, and certain compounds display surprisingly lowtoxicity to marine organisms. The deter gent actives are sulfated glycolor polyglycol half esters of alkyl or alkenyl succinic acids orwater-soluble salts thereof, wherein the alkyl or alkenyl group containsfrom about 14 to about 22 carbon atoms and the glycol moiety of theester contains from 1 to 4 units of 2 to 4 carbon atoms and the sulfategroup is terminally attached to the glycol or polyglycol chain. Thepreferred glycol units contain two carbon atoms.

While the compounds disclosed above have good detergency and low fishtoxicity levels consonant with most of the available detergents such aslinear alkylbenzene sulfonate, a preferred embodiment of the inventionhaving, along with excellent detergency, surprisingly low fish toxicitylevels is represented by the class of compounds of the followingformula:

in which R, and R are substantially linear saturated or unsaturatedaliphatic groups of 2 to 19 carbon atoms, 1

R is alkylene of 2 to 4 carbon atoms, u, v, x and y are 0 or 1, z is aninteger 1 to 4, M is H or a water-soluble v salt-forming cation, the sumof the carbon atoms in R and R is from about 13 to 21 carbon atoms, thesum of unsaturated sites in R and R is 0 to 1, the sum of u and v is 1,the sum ofx and y is l, and the sum of u and x is 1.

Thus the preferred compounds are preferably derived from hydrocarbylsuccinic anhydrides wherein the attachment of the succinic moiety to thehydro carbyl group is at carbon atoms other than the l and 2 carbonatoms of the hydrocarbyl chain. Such attachment as used in thisapplication is defined as central attachment. Bonding at carbon atoms 1and 2 of the hydrocarbyl group is defined as end attachment.

In an additional preferred embodiment z is an integer of 1 to 3,preferably 1 to 2, most preferably 2, and R is ethylene. It is furtherpreferred that the sum of carbon atoms in R, and R is from to 17. Thus,the preferred materials are sulfate salts of half esters produced byreacting ethylene glycol or diethylene glycol with an alkyl or alkenylsuccinic anhydride having 16 to 18 carbon atoms in the side chain. Thediethylene glycol derivative is most preferred as is the alkylderivative.

The hydrocarbyl radicals illustrated in the formula by R,R CH- includesuch groups as tetradecyl, pentadecyl, hexadecyl, heneicosyl, docosyl,tetradecenyl, pentadecenyl, hexadecenyl, heneicosenyl and docosenyl.

Typical compounds illustrating R R and R are listed as follows:

DESCRIPTION OF THE PREFERRED EMBODIMENTS The salt-forming cation M maybe any of numerous materials such as alkali metal, alkaline earth metal,ammonium, or various organic cations. Examples of suitable organiccations include nitrogen-containing organic cations such asdiethanolammonium and triethanolammonium cations. The alkali metalcations are preferred, and sodium ions are particularly preferred.

The alkyl and alkenyl groups which are attached to the succinic moietymay be branched or linear, although the substantially linear materialsare preferred. By substantially linear is meant that the presence of arandom methyl group, for example, somewhere on the chain will not bedetrimental to their ability to be degraded. The preferred alkyl groupsthus include the linear alkyl from tetradecyl to docosyl and the alkenylgroups will likewise be the linear materials from tetradecenyl todocosenyl.

The succinic anhydridge precursors are preferably derived by thealkylation of maleic anhydride with a monoolefin to form alkenylsuccinic anhydride followed in the case of the alkyl substitutedmaterials by hydrogenation. The olefins may be derived from any source,examples being those derived from the cracking of waxes (alpha olefins)or those derived by dehydrogenation or halogenation-dehydrohalogenationof appropriate paraffin fractions. From a commercial standpoint olefinsderived by various dehydrogenation processes are preferred.

The reaction of olefin with maleic anhydride is performed asconventionally described in the art by contacting the anhydride with atleast an equimolar amount, preferably an excess of olefin, usually atelevated temperatures, to form the desired anhydride.

The alkenyl materials may be converted to alkyl succinic anhydrides byconventional hydrogenation techniques. Alternatively and preferably, thehydrogena- 4 tion is carried out with the half ester. Hydrogenation maythus be carried out in the presence of conventional catalysts such asplatinum, platinum on inert supports, palladium, etc.

The alkenyl or alkyl succinic anhydride is reacted with an appropriatequantity ofa lower glycol or lower polyglycol to yield the half ester.An approximately stoichiometric amount of the glycol or polyglycol willcleave the anhydride ring to form the desired compound having a freecarboxyl group and a hydroxyl group on the glycol or polyglycol portionof the molecule. The use of an excess of the glycol is preferred.

Sulfation of the glycol substituted half ester to produce the acidprecursor of the compound is accomplished by any appropriate sulfationmethod, such as with oleum, sulfuric acid, or chlorosulfonic acid.

The mixed carboxylic, sulfuric acid produced is reacted with anappropriate base in order to give the detergent-active salt which thenmay be compounded to form the desired detergent composition.

The preferred detergents contain one or two ethylene glycol units. Fishshow markedly high tolerance to these materials. In addition, thepreferred compounds contain a succinic moiety which is centrallyattached on the hydrocarbyl chain.

The glycols which are precursors of the preferred compounds arerepresented by the formula in which Y is H or a water-solublesalt-forming cation, p is l to 4, R and R are substantially linearsaturated or unsaturated, unsubstituted aliphatic groups of 2 to 19carbon atoms, R is alkylene of 2 to 4 carbon atoms, u, v, x and y are 0or 1, the sum of the carbon atoms in R and R is from 13 to 21 carbonatoms, the sum of the unsaturated sites in R and R is 0 to l, the sumofu and v is l, the sum ofx and y is 1, and the sum ofu and x is 1. Inthe preferred precursor the sum of the carbon atoms in R and R is 15-17,and p is l to 2, preferably 2; and R and R are alkyl.

The following examples illustrate the preparation of the detergentactive materials of this invention.

EXAMPLE 1 Preparation of Octadecenyl Succinic Anhydride by vapor phasechromatography:

lsomer Percent Z-attachment 4.5 3-attachment 6.4 4-attachment l 1.1S-attachment 18.5 6,7,8,9-attachment 59.3

This represents a product having 95.5% central attachment.

EXAMPLE 2 Hydrogenation of Octadecenyl Succinic Anhydride g. (0.057moles) of octadecenyl succinic anhydride, 1 14 g. of n-hexane and 1 g.of 5% palladium on carbon were charged to a pressure vessel. The mixturewas stirred and heated to 50C. The'initial hydrogen pressure was 60 psi.When the pressure dropped to 50-50 psi, the system was repressured to 60psi. This process was repeated until the hydrogen uptake essentiallyceased. The mixture was filtered and the hexane was evaporated. 19.7 g.(98.5% yield) of crude octadecyl succinic anhydride was recovered.

EXAMPLE 3 Preparation of Diethylene Glycol Half Ester of OctadecenylSuccinic Acid 238.0 g. of diethylene glycol (2.25 moles) and 26.3 g. ofa linear octadecenyl succinic anhydride (0.0747 mole) prepared as inExample 1 was placed in a vessel and stirred and heated rapidly to150-160C. The solution was maintained at that temperature for 1 hour,then it was cooled to room temperature. A 250-ml. portion of ether wasadded, and the layers were separated. Then 250 ml. of ether and 125 ml.of water were added to the glycol layer. After extraction, the layerswere separated.

Each of the ether layers was extracted three times with about 100 ml.portions of water. The ether layers were combined, dried over sodiumsulfate, filtered and evaporated to give 34.1 g. of product. Thisrepresented a 99% yield of the diethylene glycol half ester.

EXAMPLE 4 Preparation of Ethylene Glycol Half Ester of OctadecenylSuccinic Anhydride The procedure of Example 3 was repeated with theexception that 177 g. of ethylene glycol (2.86 moles) and 25.0 g. ofoctadecenyl succinic anhydride (0.0714 mole) were employed. The yield ofproduct was 95%.

EXAMPLE 5 Hydrogenation of Diethylene Glycol Half Ester of OctadecenylSuccinic Anhydride 9.12 g. (0.02 mole) of a diethylene glycol half esterof octadecenyl succinic acid was dissolved in 42 ml. of n-hexane in ahydrogenation vessel. 1 g. of 5% palladium on carbon was added. Themixture was magnetically stirred and heated in a 50C. water bath. Theinitial hydrogen pressure was 60 psi. When the pressure dropped to 30-40psi, the system was repressured to 60 psi. This process was repeateduntil the theoretical hydrogen uptake was obtained. The mixture was thenfiltered and the hexane was evaporated. 14.9 g. (99% yield) ofdiethylene glycol half ester of octadecyl succinic acid was recovered.Infrared and nuclear mag netic resonance analysis were consistent withthe assigned structure and showed that the product was completelysaturated.

6 EXAMPLE 6 Sulfation of the Diethylene Glycol Half Ester of OctadecylSuccinic Acid 2.13 g. (0.00465 mole) of the diethylene glycol half esterof octadecyl succinic acid was dissolved in 100 ml. of dry ether. A 4.44g. portion (0.0381 mole) of chlorosulfonicacid was added dropwise at arapid rate. The temperature of the reaction mixture was kept at l015C.during the addition of the acid. When all of the acid was added, thecooling bath was removed, and the solution was allowed to warm to roomtemperature over a period of 20-30 minutes.

Sufficient 0.5 N NaOH was added to about ml of water to bring the pH tol 1-l2. The solution was cooled to 5- 10C., and the pH was maintainedbetween 8 and 12 by alternate addition of the acid-containing ethersolution and 0.5 N NaOH. At a final pH of 8.5, the mixture was partiallyevaporated to remove ether. The remaining solution was diluted to aknown volume. An aliquot was taken for a Hyamine titration. and theamount of active sulfate was determined. The yield of disodium'salt ofsulfated diethylene glycol half ester of octadecyl succinic acid was87%.

EXAMPLE 7 Sulfation of an Ethylene Glycol Half Ester of OctadecenylSuccinic Acid The procedure of Example 6 was repeated with the exceptionthat 2.20 g. (0.00533 moles) of an ethylene glycol half ester ofoctadecenyl succinic acid and 5.03 g. of chlorosulfonic acid (0.043moles) were used.

A hyamine titration of an aliquot from a known volume of solution whichcontained the product gave a 104% yield of anionic active.

Acid hydrolysis of this crude product indicated that the yield of thedisodium salt of sulfated half ester of ethylene glycol and octadecenylsuccinic acid was 92%, and the yield of a sulfonated-sulfated by-productwas 6%.

Other compounds were prepared by essentially the same procedures asabove. These are listed in Table 1.

TABLE 1 DlSODlUM SALTS OF EX. SULFATED DIETHYLENE YIELD CENTRAL NO.GLYCOL HALF-ESTERS (7r) ATTACH. 1%)

8 Hexadecyl 93 95 9 Hexadecyl 94 0 l0 Heptadecyl 89 91 1 l Nonadecyl 8694 1 2 Pentadecenyl 13 Hexadecenyl 84 95 14 Hexadecenyl 72 0 15Heptadecenyl 86 91 16 Octadecenyl 95 17 Nonadecenyl 73 94 I8 Eicosenyl83 19 C's-C". (saturatedyn 39 94 20 C Cm (unsaturated 93 21 C -C2"(unsaturated) 5 22 C -Cm (unsaturatcdW 93 23 C -C (unsaturated 93 24Hexadecyl 95 25 Heptadecyl 91 26 Octadecyl 91 27 Octadecyl 96 75 28Octadecyl 97 0 29 Nonadecyl 92 94 30 Eicosyl 83 31 Hep tadecenyl 91TABLE l-continued DlSODlUM SALTS OF "'A blend of approximately equalamounts of each isomer.

*A blend having a ratio of :40:30 for isomers of increasing molecularweight, respectively.

'A blend having a ratio of 26:29:27z18 for isomers of increasingmolecular weight.

respectively. 15

EXAMPLE 37 Drying of Disodium Salt of the Half Ester of C C, AlkylSuccinic Acid A portion of disodium salt of the half ester of C -C alkylsuccinic acid was dried on a small scale drum dryer under lbs. of steamabsolute (about 125C.) The product was crushed and screened to give aprod- 25 uct which was a free-flowing white powder when dry.

The sulfation products contain varying amounts of by-produets in therange of about 1 to 20%. The alkenyl derivatives have the greaterquantity of by-products, about 10 to 20%, whereas the alkyl derivativeshave lesser amounts, about 1 to 10%. These by -products may be removedby various purification processes such as extraction, chromatography,etc., but in the present examples they were left in the products becausethese by-products will normally be present in commericial materials madein accordance with this invention. Consequently, detergency and toxicitymeasurements reported herein are representative of potential commercialproducts. Each product was analyzed for detergent active material by themethod of House and Darragh, Anal. Chem., 26, 1492 (1954). Test sampleswere prepared for fish toxicity measurements and for detergencyeffectiveness using the previously determined surface active values fordetermining test concentrations.

Detergency of the compounds of the present invention is demonstrated bya miniature Terg-O-Tometer Test. In this test the effectiveness of thedetergents is measured by their ability to removed natural sebum soilfrom cotton cloth. By this method, small swatches of cloth, soiled byrubbing over face and neck, are washed with test solutions of detergentsin a miniature laboratory washer. The washer employed is so constructedthat two standard formulations and two test formulations can be used towash different parts of the same soiled swatch. This arrangement ensuresthat all formulations are working on identical soil. The quantity ofsoil removed by this washing procedure is determined by measuring thereflectances of the new cloth, the soiled cloth, and the washed cloth,the results being expressed as per cent soil removal. Because ofvariations in degree and type of soiling, in water and in cloth, andother unknown variables, the art has developed the method of usingrelative detergency ratings for comparing detergent effectiveness.

The relative detergency ratings are obtained by comparing andcorrelating the percent soil removal results from solutions containingthe detergents being tested with the results from two defined standardsolutions.

The 'two standard solutions are selected to represent a detergent systemexhibiting relatively high detersive characteristics and a systemexhibiting relatively low detersive characteristics. The systems areassigned detergency ratings of 6.3 and 2.2, respectively.

By washing portions of each soiled cloth with the standardizedsolutions, as well as with two test solutions, the results can beaccurately correlated. The two standard solutions are identical informulation but are employed at different hardnesses.

Standard Solution Formulation lngredient Weight "/2 Linear Alkylbenzenesulfonate (LAS) 20 Sodium tripolyphosphatc 40 Water 8 Sodium Sulfate 24Sodium Silicate 7 Carboxymethylcellulose l A further refinement in thedetermination of relative detergency ratings was developed. In thismethod, instead of employing two standard formulations, one of theformulations used as one of the four test solutions had a known relativedetergency rating (RDR) which had been determined by the above formula.Relative detergency ratings of the other three formulations were thendetermined by comparing the percent soil removal (SR) of theseformulations with that of the known formulation.

Detergency results obtained on a variety of the subject compounds aregiven in the following table. Each valueshown is the average of at leastfour tests. For comparison, the detergency rating is given for a linearalkylbenzene sulfonate (LAS) (having from 10 to 13 carbon straight chainalkyl groups) both with and without phosphate builder (sodiumtripolyphosphate).

Each formulation tested comprised 25 weight percent of the test materialalong with 1% carboxymethylcellulose, 7% sodium silicate, 8% water, andsufficient sodium sulfate to make The LAS comparison formulations wereprepared in the same way except that in Test 1 20% of LAS and 35% ofsodium tripolyphosphate were used. The formulations were tested at aconcentration in water of 0.10 and 0.15 weight percent. The test resultswere obtained at a pH of 9.5.

TABLE II TEST At 0.1% (WL) Conc. At 0.15% (Wt) Cone.

NO. COMPOUND TESTED 50 ppm 100 ppm 180 ppm 50 ppm 100 ppm 180 ppm 1 LASwith phosphate 5.8 3.9 1.7 6.3 6.2 4.1 2 LAS without phosphate 2.6 1.30.0 3.9 2.4 0.9 3 Product of Ex. No. 14 6.1 5.0

As can be seen from these data, the compositions of this invention arehighly effective as heavy duty laun dering agents. Their effectivenessis comparable to conventional LAS with phosphate and surprisingly moreeffective than LAS without phosphate builders.

In order to determine the tolerance of fish for the detergent activecompounds of this invention the following routine bioassay method wasemployed: Standard Methods for the Examination of Water and WasteWater", American Public Health Association, pages 458-471, 1 1th Edition1960). The test is performed as follows: For each test concentration a5-ga11on jar containing 10 liters of tap water dechlorinated by airblow- TEST 72 hours and 96 hours. The test concentrations are based ondecilog intervals, and the 96-hour median tolerance limit (TL P isobtained for graphical or arithmetic interpolation between the highestconcentration with more than survival and the lowest concentration withless than 50% survival. I

It was found in these tests that those compounds having centralattachment of the succinic ester portion of the molecule to thehydrocarbyl chain were surprisingly less toxic than the compounds havingend chain attachment. Table III contains data comparing the toxicity ofcompounds having central and end chain attachments.

TABLE III FISH TOLERANCE CENTRAL END CHAIN TL COMPOUND TESTED ATTACH.(%)ATTACH.(%) (PPM) Product of Ex. No. 28 0 100 0.

ing was prepared. The test surfactant is added and 10 sticklebacks(Gasterosteidae) are transferred from a fresh water holding tank to thejar. Dead fish are counted and removed at 6 hours, 24 hours, 48 hours,

Data from a representative number of other compounds of this inventionare set forth in the following table. These data are compared with theTL,,, values for LAS and other conventional detergents.

TABLE IV FISH TOLERANCE TABLE IV-continued FISH TOLERANCE "Allnon-commercial compounds have about 91-95% central attachment. excepttest No. 25 which has 83% central attachment. *Commercial product. "Runin ppm hardness (otherwise precipitates with hardness) These data showthat the TL, values for most of the compounds of this invention,particularly those having internal attachment are surprisingly higherthan the linear alkylbenzene sulfonate.

The degree of degradation under conditions such as are encountered incesspools and septic tanks for the compounds of this invention weredetermined by tests set forth in Microaerophilic Biodegradation ofTallow-Based Anionic Detergents in River Water, E. W. Maurer, T. C.Crodon, and A. J. Stirton, The Utilization Res. Dev. Div., ARS, USDA,Philadelphia, Pennsylvania, JAOCS, Volume 48, Page 163 (1971). Themicroaerophilic test procedure described in this article was employedwith the exception that a bacterial seed of filtered primary sewageanaerobic digester mix) was employed, the test was operated at roomtemperature and, in contrast to the results obtained by the authors, asmall amount of degradation was observed in each case for linearalkylbenzene sulfonate.

Data in the following table show the degradation perfomiance of thecompounds of this invention in this test. The amount of surfactant inpercent remaining after 2, 3, 5 and 6 days deten'nined by standardmethylene blue analysis is set forth.

TABLE V MlCROAEROPl-llLlC TEST organic and inorganic alkali metal andalkaline earth metal salts such as inorganic sulfates, carbonates, orborates. Also nonphosphate builders may be included in the composition.Also small quantities of phosphate builders may be included in thecompositions, although, of course, they are not necessary for effectivedetergency.

While the character of this invention has been described in detail withnumerous examples, this has been done by way of illustration only andwithout limitation of the invention. It will be apparent to thoseskilled in the art that modifications and variations of the illustrativeexamples may be made in the practice of the inven tion within the scopeof the following claims.

We claim:

1. A surface active compound of the formula:

Percent Active Remaining After Elapsed Time in which R and R aresubstantially linear alkyl groups of 3 to 19 carbon atoms, u, v, x and yare 0 or 1, M is H or an alkali metal, alkaline earth metal, or ammoniumcation, the sum of the carbon atoms in R, and R is 13 to 21, the sum ofu and v is l, the sum ofx and y is l, and the sum ofu and x is l.

2. The compound of claim 1 in which the sum of the carbon atoms in R andR is from 15 to 17.

3. The compound of claim 1 in which M is alkali metal.

4. The compound of claim 3 in which M is sodium.

1. A SURFACE ACTIVE COMPOUND OF THE FORMULA:
 2. The compound of claim 1in which the sum of the carbon atoms in R1 and R2 is from 15 to
 17. 3.The compound of claim 1 in which M is alkali metal.
 4. The compound ofclaim 3 in which M is sodium.